The macromolecular organization of the secondary wall of the cells from tree xylem is in large part responsible for the mechanical and physiological properties of wood. Modeling secondary walls of wood is difficult because information about their macromolecular architecture at the ultrastructural scale is missing. Numerous microscopic studies have provided views of the lignocellulosic composite material, but nanoscale distribution of the polymers and their interaction in muro is still not clearly understood. The intimate macromolecular organization of cell walls is defined during their differentiation. It is at the stage of wall thickening corresponding to secondary wall development that the topochemical organization and the interactions between cellulose, hemicelluloses and lignin are established.Using the conjunction of the high resolution of transmission electron microscopy (TEM) and the specificity of immunological probes directed against the main cell wall polymers, we investigated the deposition of hemicelluloses and lignins from the early stage of cambium differentiation to the mature fiber and vessel walls in growing model plants of Arabidopsis thaliana and poplar. TEM examination of differentiating cells as well as various wood and wood -derived materials and genetic plant mutants brought multiple evidence of the lamellar sub-organization of the secondary walls. Immuno-gold labeling showed that two structurally different xylan types were deposited at different stages in the wall thickening. Similarly two different types of lignin molecules were shown to be differentially polymerized at different steps of the building of the wall, lignin molecules of the condensed type being first deposited at the earliest stage of secondary thickening before the non-condensed types. This process may be modified in response to environmental factors, as in tension wood.The spatio-temporal relationships occurring between hemicelluloses, lignin and cellulose microfibrils (CMFs) during the secondary wall development suggest that xylans with less substituted chains would be more directly interacting with CMFs than those with higher substitution patterns. It also suggests that lignin molecules of the non-condensed type have a function in bringing cohesion between the lamellae of CMFs. A model of wall assembly during secondary thickening is proposed.

Due to the high potential of cellulose nanoparticles in composite materials and for both fundamental and technological considerations, we investigated the interaction between microfibrillar cellulose and fibers. The contribution to the paper properties of fines added to a pulp suspension was determined. The impact of various proportions of fines added to a softwood kraft pulp on the paper strength and how they affected porosity and density was evaluated. The respective effects of dried fines (dead fines), originating from paper or board degradation, and the newly formed secondary fines (fresh fines) generated during refining were examined. The nature of the bonding between the fines and the fibers versus physical retention was characterized in the pulp suspension. For the first time the respective parts in the interaction of hydrogen bonds and mechanical associations were demonstrated and quantified. The amount of H-bonded fresh fines exceeded that of dead fines by more than 30 %. The results revealed that, for both types, the amount of H-bonded fines reached a threshold, independently of the proportion of fines added to the fibers. Addition of fines significantly affected the porosity of papers, fresh fines decreasing porosity more readily than dead fines. All the results are convergent to indicate that fresh fines penetrate more evenly and more deeply into the fiber network and induce better bonding that produces a closure of the fiber mat structure. They also demonstrate that incorporating an optimal proportion of fresh cellulose fines in fiber networks can bring significant improvement to the final composite material.

The composition and ultrastructural arrangement of cell wall polymers in wood fibres have determining influence on the properties of wood derived materials. It is therefore important to improve our understanding of the relationship between fibres organisation, the modifications induced by pulping treatments, and the resulting paper sheet mechanical properties. The different treatments to which fibres are subjected during the manufacturing of pulps and papers induce morphological and micro-structural alterations due to the removal of wall constituents and of microfibrillar elements. The impact of pulping processes on fibres was investigated at the ultrastructural scale of transmission electron microscopy. Particular attention was given to the effects of beating in refiners at various intensities on the ultrastructure of fibres. The most characteristic effects consisted of delaminations, microfibril disorganisation, and even fractures, of varying importance depending on the intensity of the mechanical refining. The consequences of internal alterations and surface modifications of the fibres were examined in relation to the paper sheet mechanical properties. Correlations between the type of alteration observed in the fibres and its possible impact on a given paper mechanical property are suggested. With similar approaches, the effects of drying and recycling were studied.Abbreviations: TEM -Transmission electron microscopy;°SR -Schopper -Riegler degree.